CN103359789A - Preparation method of bismuth subcarbonate - Google Patents
Preparation method of bismuth subcarbonate Download PDFInfo
- Publication number
- CN103359789A CN103359789A CN2013103197360A CN201310319736A CN103359789A CN 103359789 A CN103359789 A CN 103359789A CN 2013103197360 A CN2013103197360 A CN 2013103197360A CN 201310319736 A CN201310319736 A CN 201310319736A CN 103359789 A CN103359789 A CN 103359789A
- Authority
- CN
- China
- Prior art keywords
- bismuth
- filtrate
- copolymer
- vinylbenzene
- polyacrylamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The method prepares bismuth subcarbonate from industrial sodium carbonate and industrial bismuth nitrate, and takes modified polyacrylamide-co-styrene-co-acrylic acid copolymer as the absorption material. Heavy metals are removed from the industrial sodium carbonate and industrial bismuth nitrate through absorption. The modified copolymer is prepared through modification of polyacrylamide-co-styrene-co-acrylic acid copolymer raw material with formaldehyde, dimethylamine and optionally selected C2-C4 organic amine containing sulfydryl, the specific reactions are that side chains of the copolymer are induced into hydroxymethyl (-CH2-OH) and aminomethyl (-CH2-N(CH3)2), and are optionally induced or not induced into sulfydryl (-SH) or sulfenyl (-S-). The modified copolymer has a relatively strong absorption ability of heavy metals such as lead, cadmium, mercury, and arsenic.
Description
Technical field
The present invention relates to the preparation method of Bismuth Subcarbonate, relate in particular to the preparation method of high purity Bismuth Subcarbonate.
Background technology
The molecular formula of Bismuth Subcarbonate or structural formula are (BiO)
2CO
31/2H
2O, molecular weight: 518.91, be white or little yellowish powder; Odorless, tasteless; Meet light namely slowly rotten.This product is insoluble in water and in the ethanol.With hydrochloric acid in gastric juice medicine and astringent, be used for gastric and duodenal ulcer and diarrhoea etc. in the Bismuth Subcarbonate conduct, also can be used for slight burn outward, ulcer and eczema etc.
Chinese patent 103011286A discloses the technique that the thick bismuth oxide of a kind of usefulness is produced bismuth subcarbonate, comprising: 1. take by weighing thick bismuth oxide-60 order 〉=95% that sieve, to the coarse particles of screen overflow after such as the grinding of ball mill class grinding plant after sieve, mixing; 2. get the thick bismuth oxide raw material after sieving, add nitric acid; To restrain/to restrain as unit, liquid-solid mass ratio is 2-20:1; Nitric acid and thick bismuth oxide raw materials quality be than 1-1.5:1, temperature of reaction 0-200 ℃ (preferred 85 ℃), preferred 4 hours of reaction times 1-48h() carry out chemical subtraction, control supernatant liquor pH0.5-1.5; Be prepared into a kind of new compound that contains the nitric acid insolubles; So that the mass percent of bi content is greater than 99% in the new compound, bismuth is less than 1g/L in the reaction soln; Press filtration separates; Contain impurity atom liquid and add the heavy bismuth of alkali with known technology, the bismuth slag returns with thick bismuth oxide raw material and mixes again chemical subtraction, perhaps send conventional pyrometallurgical smelting to do bismuth ingot and reclaims; The heavy bismuth waste liquid that produces discharges through environmental protection treatment again; 3. the filter cake with press filtration adds excessive nitric acid, dissolve complete, and the mass ratio of control nitric acid and filter cake is 0.5-5:1, temperature 0-100 ℃; Filter, the nitric acid insolubles after the filtration send conventional pyrometallurgical smelting to do reductive agent or fuel; Sour lixiviation liquid after the filtration adds sodium carbonate solution and carries out metathesis, is 8.5～9.0 at pH, 50～55 ℃ of lower reactions of temperature 40 minutes, generates Bismuth Subcarbonate, obtains finished product through washing, centrifugation, oven dry, pulverizing again; 4. the SODIUMNITRATE mother liquor after separating is through the concentration and recovery SODIUMNITRATE.
Chinese patent CN101628735A discloses a kind of preparation method of bismuth-series chemical product, and the method comprises the bismuth meal that smart bismuth meal is changed into-60 order 〉=90%; Above bismuth meal is interspersed among in the burning dish, pass into air with the bismuth meal low-temperature oxidation under 200～800 ℃ temperature, then cooling is taken out, and obtains the regular grade bismuth oxide powder; Above regular grade oxidation bismuth meal is mixed with carbonate solution, under 5～160 ℃ temperature, react, obtain Bismuth Subcarbonate.
Because the pharmaceutical grade bismuth subcarbonate is very high to the requirement of impurity, therefore exist demand for the preparation method of high purity chemicals level Bismuth Subcarbonate in the art.
At present, for the mineral compound raw material for preparing pharmaceutical grade or food grade from the industrial mineral compound raw material that contains the impurity such as heavy metal, usually use precipitation and filter method, charcoal absorption method to remove heavy metal wherein, still, the effect of removing of heavy metal has much room for improvement.In addition, use gac, the effect of Adsorption of Heavy Metals is general, and the regeneration expense of gac is higher.
In the prior art for from the industrial sodium carbonate in various sources, the Bismuth Subcarbonate product of industrial nitric acid bismuth production high purity (pharmaceutical grade or food grade), still do not have effectively, thoroughly to remove heavy metal such as the method for lead, cadmium, nickel, copper, mercury, the heavy metal arsenic that especially exists with anionic form (arsenate or arsenite) more is difficult to remove up hill and dale.
In the prior art a lot of bibliographical informations are arranged various polymeric adsorbents be used for Adsorption of Heavy Metals.
For example, CN102764522A discloses a kind of organic floculant, and it contains the component of following weight part: 20～30 parts of 10～20 parts in formaldehyde, 10～20 parts of dimethylamine, 40～50 parts of polyacrylamides, 30～40 parts of styrene sulfonates, 20～30 parts of ligninsulfonates and benzene olefin(e) acids.Flocculant formula of the present invention is reasonable, method for making is simple, with low cost, easy to operate when using, have advantages of safety, environmental protection, nontoxic, result of use good.
CN102398980A discloses a kind of compound for treatment of electroplating wastes, is comprised of calcium hydroxide, polyacrylamide, formaldehyde.
But some polymeric adsorbent product of prior art is acid and alkali-resistance not, and is limited for the adsorptive power of heavy metal in addition.Especially, at interfering ion such as the Mg of high density
2+, Al
3+, Ca
2+And Cl
-, SO
4 2-, CO
3 2-Existence under, these resins are unsatisfactory such as the selective adsorption of lead, cadmium, nickel, copper, mercury for heavy metal ion.
Summary of the invention
According to the first embodiment of the present invention, provide the method for preparing Bismuth Subcarbonate from industrial sodium carbonate and industrial nitric acid bismuth, the method comprises:
(A), feed purification is processed:
A1) industrial sodium carbonate is dissolved in the deionized water (for example reaching 2-30wt%, preferred 4-25wt%, more preferably 6-22wt%, further preferred 8-20wt%, the more preferably concentration of 10-17wt%), with activated carbon decolorizing, the removal of impurity, filters and obtain filtrate 1; Randomly, then in the filtrate 1 that obtains, add the polyacrylamide of modification-co-vinylbenzene-co-acrylic copolymer as sorbing material, by the Adsorption heavy metal; Again filter, obtain to contain the purifying filtrate 1 ' of yellow soda ash;
A2) the industrial nitric acid bismuth is dissolved in rare (0.1-5wt% concentration for example, more preferably 0.3-3wt% concentration, such as 0.5-1wt% concentration) salpeter solution in (for example reach 2-30wt%, preferred 4-25wt%, more preferably 6-22wt%, further preferred 8-20wt%, more preferably the Bismuth trinitrate concentration of 10-17wt%), with activated carbon decolorizing, the preliminary removal of impurity, filter and obtain filtrate; Then in filtrate, add the polyacrylamide of modification-co-vinylbenzene-co-acrylic copolymer as sorbing material, by the Adsorption heavy metal; Again filter, obtain to contain the purifying filtrate 2 of Bismuth trinitrate;
(B), Bismuth Subcarbonate is synthetic:
Mol ratio according to yellow soda ash and Bismuth trinitrate is 6:1 to 3:2 (preferred 5:1 to 3.5:2, more preferably 4:1 to 2:1), filtrate 1 or filtrate 1 ' are joined in the reactor with filtrate 2, ((for example be warming up to 45-70 ℃ in intensification, such as 55 ℃)) or situation about not heating up under, in the pH scope of 7.5-12 (preferred 8-11.5, more preferably 9-11), stir and reacted (for example 10-50 minute, such as 20 minutes), formation contains sedimentary mixture;
(C), aftertreatment:
Carry out rinsing to containing sedimentary mixture, drying is pulverized, and obtains Bismuth Subcarbonate (BiO)
2CO
31/2H
2The O solid product;
Step (A) substep a1) or a2) in employed modified copolymer (abbreviation resin) be by with formaldehyde and dimethyl amine and the optional C2-C4 organic amine that contains sulfydryl (such as aminoothyl mercaptan, monomethyl aminoothyl mercaptan, an ethylamino sulfur alcohol, aminopropan mercaptan, amino butyl sulfhydryl etc.) polyacrylamide-co-vinylbenzene-co-acrylic acid copolymer raw material being carried out modification, at the side chain of multipolymer (such as amido linkage (CO-NH
2) amino) the upper methylol (CH that introduces
2-OH) and amine methyl (CH
2-N (CH
3)
2), and randomly the side chain of multipolymer introduce or do not introduce sulfydryl (SH) or sulfenyl (S-), obtain.
The reaction formula of preparation Bismuth Subcarbonate is as follows:
4Bi（NO
3）
3·5H
2O＋6Na
2CO
3·H
2O→2（BiO）
2CO
3·1/2H
2O＋12NaNO
3+4CO
2+5H
2O
Wherein Bismuth Subcarbonate forms as throw out.
Preferably, carry out repeatedly rinsing in step (C), the pH value that makes washing water is till (preferably between 8-10, for example 8.5) between the 7.5-11.
Generally, the addition of modified copolymer is the 1-20wt% that is equivalent to the total consumption of industrial sodium carbonate in substep (a1), preferred 3-15wt%, more preferably 4-10wt%, further preferred 5-8wt%, 6wt% for example, 7wt%, 8wt%.Concrete addition can easily be determined according to the content of heavy metal in the industrial sodium carbonate by those of skill in the art.
In addition, the addition of modified copolymer is the 1-40wt% that is equivalent to the total consumption of industrial nitric acid bismuth in substep (a2), preferred 5-35wt%, more preferably 8-30wt%, further preferred 10-25wt%, 15wt% for example, 18wt%, 20wt%.Concrete addition can easily be determined according to the content of heavy metal in the industrial nitric acid bismuth by those of skill in the art.
Preferably, weight ratio (the acrylamide: vinylbenzene: vinylformic acid) be: 70-90:7-22:1-5 of three kinds of monomers of the polyacrylamide of modification-co-vinylbenzene-co-acrylic copolymer, be preferably 73-87:10-18:1.5-4.5, more preferably 76-84:12-16:1.8-3.5, for example 83:15:2.The effect that a small amount of carboxyl that exists in multipolymer has pre-concentration or assembles for metal ion, but do not have the ability of ion-exchange, therefore, the interference-free ion of multipolymer is (such as Mg
2+, Ca
2+And Cl
-, SO
4 2-, CO
3 2-) impact.
Preferably, the methylol (CH that contains 0.5-15wt% (preferred 3.0-12wt%, more preferably 4.0-8.0wt%) in the modified copolymer
2-OH) and the amine methyl (CH of 0.5-15wt% (preferred 3.0-12wt%, more preferably 4.0-8.0wt%)
2-N (CH
3)
2), and optional, 0% or the sulfydryl of 0.5-6wt% (preferred 1.0-4wt%, more preferably 1.5-3.0wt%) (SH) or sulfenyl-S-, based on the gross weight of multipolymer.When contain nitrogen (N) and sulfydryl (SH) or sulfenyl-during S-, be particularly suitable for Adsorption of Mercury IONS OF H g
2+Or mercury metal.
Further more preferably, also contain in the above multipolymer or load the Fe of 0.2-5wt% (preferred 0.5-4wt%, more preferably 1.0-3.0wt%)
3O
4, MnO
2And/or ZrO
2, i.e. a kind of, any two or three in three kinds of metal oxides.This multipolymer is particularly suitable for adsorbing magneticmetal and heavy metal.The existence of these metal oxides can be by ligand complex effect and the heavy metal ion adsorbed combination of dentate, and these absorption are specific internal layer absorption, do not allow to be subject to the impact of ionic strength and interfering ion.In addition, these metal oxides usually are both sexes, under different pH values with electric charge change to some extent, therefore can either the Adsorption of Heavy Metals positively charged ion, also can Adsorption of Heavy Metals negatively charged ion (arsenate and arsenite).For example forming the manganous arsenate throw out is adsorbed by multipolymer.
Fe
3O
4, MnO
2And/or ZrO
2Load on the above-described modified copolymer, can Adsorption arsenic.MnO for example
2The principle of absorption pentavalent arsenic main with pentavalent arsenic form and Manganse Dioxide with electric charge relevant, the generation electrostatic interaction; The absorption trivalent arsenic then first is oxidized to pentavalent arsenic by Manganse Dioxide with it, generates simultaneously Mn
2+, pentavalent arsenic not only can with the Manganse Dioxide generation electrostatic interaction that is not reduced into Mn2+, also can form manganous arsenate precipitation with Mn2+.
The weight-average molecular weight of multipolymer or modified copolymer is in 5-40 ten thousand (dalton) scope, preferably in 8-35 ten thousand scopes, and for example 12,18,20,25,30.Most preferably 10-15 ten thousand.
Multipolymer of the present invention has avoided the interfering ion of high density (such as Mg by effect Adsorption of Heavy Metals such as static, south, road film effect, coordination or complexings
2+, Al
3+, Ca
2+And Cl
-, SO
4 2-, CO
3 2-) interference effect.
Be used for the present invention's industrial nitric acid bismuth raw material or industrial carbonic acid sodium raw materials and usually contain the heavy metal of the content that can not ignore (for example 0.001-0.01wt%, 0.0015-0.008wt%, 0.002-0.006wt%) such as lead, cadmium, nickel, copper, mercury and/or arsenic.These heavy metals generally exist with ionic species.Content depends on the source of these industrial raw material products.Even, industrial nitric acid bismuth raw material or industrial carbonic acid sodium raw materials contain 0.002-0.02wt% usually (such as 0.003-0.015wt%, lead 0.005-0.01wt%), cadmium, nickel, copper and/or mercury, and 0wt% or 0.001-0.01wt% (such as 0.003-0.008wt%, 0.005-0.006wt%) arsenic.For example, use the prepared industrial sodium carbonate of mine salt, or the industrial sodium carbonate that from field of inorganic chemical engineering, reclaims as byproduct, and not through the industrial nitric acid bismuth coarse raw materials of purification, be exactly the situation of this content.
Described " high purity " Bismuth Subcarbonate (BiO) in this application
2CO
31/2H
2O refers to pharmaceutical grade or food grade, refers in particular to the Bismuth Subcarbonate (BiO) that purity is higher than 99.5%, heavy metal content is lower than limit of detection
2CO
31/2H
2O.
" choose " in this application expression wantonly and be with or without, or expression is carried out or do not carried out.
According to the most preferred embodiment of the present invention, a kind of method for preparing above-mentioned modified copolymer is provided, it comprises:
1) preparation of polyacrylamide-co-vinylbenzene-co-acrylic copolymer (multipolymer I, i.e. P (AM-St-AA))
Monomer acrylamide, vinylbenzene and vinylformic acid according to 70-90:7-22:1-5, are preferably 73-87:10-18:1.5-4.5, and more preferably the weight ratio of 76-84:12-16:1.8-3.5 is mixed the monomer mixture that forms 100 weight parts.Then in the reactor of the deionized water that the 300-700 weight part is housed, add the 15-30wt% of above-mentioned monomer mixture, add emulsifying agent or do not add emulsifying agent, pass into nitrogen and carry out mechanical stirring, be warming up to 40-60 ℃, add peroxide initiator, then under agitation carry out polyreaction, form seed emulsion (namely, without the emulsion of soap, the self-emulsifying system).Then the temperature in seed emulsion is maintained under 40-60 ℃, be added drop-wise to remaining monomer mixture in the seed emulsion and time for adding is 2-5 hour, and when beginning to drip monomer mixture, will be dissolved in by other peroxide initiator in the deionized water formed initiator solution and be added drop-wise to lentamente in the seed emulsion and time for adding is 1-3 hour.All monomer mixtures further are warmed up to 62-70 (for example 65 ℃) after dripping and finishing, and continue reaction 2-5 hour, the sampling and measuring solid content.
Reaction separates with supercentrifuge after finishing, and washs with deionized water.Then carry out drying under reduced pressure, pulverize, obtain by the molecular powder of microspheroidal grain, be i.e. polyacrylamide-co-vinylbenzene-co-acrylic copolymer (being called for short multipolymer I).
2) preparation of the polyacrylamide of modification-co-vinylbenzene-co-acrylic copolymer (multipolymer II)
The multipolymer I of 50 weight parts is dissolved in 40-60 ℃ the deionized water of 300-700 weight part and forms mixture, regulate the pH value between the 8-9 with caustic alkali sodium hydroxide (or using calcium hydroxide), add a small amount of Potassium Persulphate or Sodium Persulfate or ammonium persulphate (or, can not add) yet, maintain the formalin solution (30-36% concentration) of the 40-60 ℃ of lower 15-30 of interpolation weight part at mixture temperature, stir lower under 40-60 ℃ temperature, the reaction for some time, add again the dimethylamine of 3-7 weight part and the aminoothyl mercaptan of 2.5-5g weight part, stirring reaction for some time under 50-55 ℃ temperature.Reaction separates with supercentrifuge after finishing, and washs with deionized water.Drying under reduced pressure 3 hours (or-60 to-70 ℃ the freeze drier lyophilize that places 2-3 days), then pulverize, obtain the powder of particulate form, namely obtain the polyacrylamide of modification-co-vinylbenzene-co-acrylic copolymer (being called for short multipolymer II).
3) adopt the in-situ chemical coprecipitation method (for example according at " magnetic high-strength polypropylene acid amides/Fe
3O
4Nanometer composite hydrogel ", Acta PhySico-Chimica Sinica, 2011,27(5), and the method for describing among the 1267-1272), in the presence of above-described modified copolymer II, introduce therein Fe by the in-situ chemical coprecipitation method
3O
4Particle, acquisition contains the Fe of 1.0-4.0wt%
3O
4The magnetic polyacrylamide of particle-co-vinylbenzene-co-acrylic copolymer.Or adopt dispersion method to obtain to contain the Fe of 1.0-4.0wt%
3O
4The magnetic polyacrylamide of particle-co-vinylbenzene-co-acrylic copolymer.
Perhaps similarly, adopt the in-situ chemical coprecipitation method, in the presence of above-described multipolymer II, introduce therein MnO by the in-situ chemical coprecipitation method
2Particle, acquisition contains the MnO of 1.0-4.0wt%
2The magnetic polyacrylamide of particle-co-vinylbenzene-co-acrylic copolymer.Or adopt dispersion method to obtain to contain the MnO of 1.0-4.0wt%
2The magnetic polyacrylamide of particle-co-vinylbenzene-co-acrylic copolymer.
Generally, the high purity Bismuth Subcarbonate (BiO) of the present invention's acquisition
2CO
31/2H
2O has following assay (100mg sample):
Advantage of the present invention or useful technique effect
Method of the present invention can obtain highly purified Bismuth Subcarbonate (BiO)
2CO
31/2H
2O.The polyacrylamide of synthesis modification of the present invention-co-vinylbenzene-co-acrylic copolymer is as sorbing material, and it has the ability of high acid and alkali-resistance.In addition, owing to not existing strong acid anion such as-SO
3 -Deng, therefore, have the freedom from jamming ion (such as Mg
2+, Al
3+, Ca
2+And Cl
-, SO
4 2-, CO
3 2-) the ability of interference, and the less impact that is subjected to ionic strength.And its regeneration is easily for example used the NaCl solution washing, but Reusability after the regeneration.There are a large amount of N, O and S element in the multipolymer of the present invention, various interactions occur between they and the heavy metal, such as static, south, road film effect, coordination, complexing etc., especially the selection of the consumption of the ratio by comonomer and properties-correcting agent, so that modified copolymer has suitable N, O and S ratio, show the highly selective to heavy metal adsorption, avoid interference simultaneously the impact of ion.So, be adapted at interfering ion and have lower highly selective Adsorption of Heavy Metals.Preferred modified copolymer of the present invention (load Fe for example
3O
4, MnO
2And/or ZrO
2Modified copolymer) simultaneously the heavy metal of Liquidity limit form is such as the arsenic (arsenate or arsenite) of lead, cadmium, nickel, copper and/or mercury and anionic form.
Description of drawings
Fig. 1 is that the multipolymer I of Preparation Example 1 is the infrared spectrogram of P (AM-St-AA).
Wherein 3060,3025cm
-1The serial absorption peak at place belongs to respectively the V in the phenyl ring
C-HStretching vibration, and 1651,1648cm
-1The absorption peak at place belongs to acid amides I band V
C-OThe V of charateristic avsorption band and carboxyl
C-OAbsorption peak, and 1544cm
-1Absorption peak belongs to the V of acid amides II band
C-HStretching vibration.
Fig. 2 is process flow sheet of the present invention.
Embodiment
Embodiment
Preparation Example 1
A) preparation of polyacrylamide-co-vinylbenzene-co-acrylic copolymer (multipolymer I, i.e. P (AM-St-AA))
With 83g monomer acrylamide, the vinylformic acid of 15g vinylbenzene and 2g mixes the monomer mixture that forms 100g.Then in the glass reactor of the deionized water that 500mL is housed, add the above-mentioned monomer mixture of 20g, pass into nitrogen and carry out mechanical stirring, be warming up to 55 ℃, add the initiator potassium persulfate of 0.5g, then under agitation carried out polyreaction 1.5 hours, the formation seed emulsion (that is, and without the emulsion of soap, the system of self-emulsifying).Then the temperature in seed emulsion is maintained under 55 ℃, be added drop-wise to the monomer mixture of remaining 80g in the seed emulsion and time for adding is 3 hours, and when beginning to drip monomer mixture, will be dissolved in by the Potassium Persulphate of 0.3g in the deionized water of 5ml formed initiator solution and be added drop-wise to lentamente in the seed emulsion and time for adding is 1.5 hours.All monomer mixtures further are warmed up to 65 ℃ after dripping and finishing, and continue reaction 3 hours, the sampling and measuring solid content.Separate with supercentrifuge after reaction finishes, and be divided into 4 times with the deionized water of 1000ml and wash.In carrying out drying under reduced pressure 3 hours at the particulate that the absolute pressure (being the vacuum tightness of 0.8Atm) of 0.2Atm is lower after will washing under 50 ℃ (or place-60 to-70 ℃ freeze drier lyophilize 2-3 days), then pulverize, acquisition is by the molecular powder of microspheroidal grain, be polyacrylamide-co-vinylbenzene-co-acrylic copolymer (being called for short multipolymer I), the GPC method records weight-average molecular weight 12.5 ten thousand.According to the solid content of sampling analysis, show that basically all monomers (96%) have all participated in reaction and entered into multipolymer.
The infrared spectrogram of P (AM-St-AA) multipolymer I is referring to Fig. 1.
B) preparation of the polyacrylamide of modification-co-vinylbenzene-co-acrylic copolymer (multipolymer IIA)
50g multipolymer I is dissolved in 55 ℃ the 500ml water and forms mixture, regulate the pH value between the 8-9 with caustic alkali sodium hydroxide (or using calcium hydroxide), the Potassium Persulphate of interpolation 0.5g (or, can not add) yet, maintain the formalin solution (35% concentration) of 55 ℃ of lower 20g of interpolation at mixture temperature, reacted 1 hour under 55 ℃ temperature under stirring, add the dimethylamine of 5g and the aminoothyl mercaptan of 3.5g again, stirring reaction is 1 hour under 50-55 ℃ temperature.Separate with supercentrifuge after reaction finishes, and be divided into 5 times with the deionized water of 1200ml and wash.In carrying out drying under reduced pressure 3 hours at the particulate that the absolute pressure (being the vacuum tightness of 0.8Atm) of 0.2Atm is lower after will washing under 50 ℃ (or place-60 to-70 ℃ freeze drier lyophilize 2-3 days), then pulverize, obtain the powder of particulate form, namely obtain the polyacrylamide of modification-co-vinylbenzene-co-acrylic copolymer (being called for short multipolymer II-A), it is approximately 130,000 that the GPC method records weight-average molecular weight.(SH) (and/or the content of sulfenyl (S-)) is about 2.08wt% with purple light spectrophotometry sulfydryl.
In addition, compare with charging capacity, by
13The C-NMR method records the methylol (CH in the multipolymer
2-OH) content is about 6.4wt% and record amine methyl (CH with the purple light spectrophotometry
2-N (CH
3)
2) content be 7.1wt%, based on the gross weight of multipolymer.
Preparation Example 2
Repeat above embodiment 1, just step B) in also added 0.2g with the formalin solution (35% concentration) of 20g the linking agent glutaraldehyde.Obtain modification and lightly crosslinked polyacrylamide-co-vinylbenzene-co-acrylic copolymer (being called for short multipolymer II-B), it is 350,000 that the GPC method records weight-average molecular weight.(content SH) is 1.95wt% with purple light spectrophotometry sulfydryl.
Preparation Example 3
Repeat above embodiment 1, just step B) in do not add aminoothyl mercaptan, add the dimethylamine of 8.5g.Obtain the polyacrylamide of modification-co-vinylbenzene-co-acrylic copolymer (being called for short multipolymer II-C), it is approximately 130,000 that the GPC method records weight-average molecular weight.(content SH) is 0wt% with purple light spectrophotometry sulfydryl.
Preparation Example 4
Employing is at " magnetic high-strength polypropylene acid amides/Fe
3O
4Nanometer composite hydrogel ", Acta PhySico-Chimica Sinica, 2011,27(5), the in-situ chemical coprecipitation method of describing among the 1267-1272 is introduced Fe therein by the in-situ chemical coprecipitation method in the presence of the modified copolymer II-A of embodiment 1
3O
4Particle, acquisition contains the Fe of 2.0wt%
3O
4The magnetic polyacrylamide of particle-co-vinylbenzene-co-acrylic copolymer II-D.
Preparation Example 5
According to embodiment 4 in similar method, adopt the in-situ chemical coprecipitation method, in the presence of the multipolymer II-A of Preparation Example 1, introduce therein MnO by the in-situ chemical coprecipitation method
2Particle, acquisition contains the MnO of 2.3wt%
2The magnetic polyacrylamide of particle-co-vinylbenzene-co-acrylic copolymer II-E.
Preparation Example 6
According to embodiment 4 in similar method, adopt the in-situ chemical coprecipitation method, in the presence of the multipolymer II-B of Preparation Example 2, introduce therein MnO by the in-situ chemical coprecipitation method
2Particle and Fe
3O
4Particle (the weight ratio 1:1 of two kinds of particles), acquisition contains the MnO of 2.5wt%
2Particle and Fe
3O
4The magnetic polyacrylamide of particle-co-vinylbenzene-co-acrylic copolymer II-F.
Preparation Example 7
According to embodiment 4 in similar method, adopt the in-situ chemical coprecipitation method, in the presence of the multipolymer II-C of embodiment 3, introduce therein MnO by the in-situ chemical coprecipitation method
2Particle, acquisition contains the MnO of 2.2wt%
2The magnetic polyacrylamide of particle-co-vinylbenzene-co-acrylic copolymer II-G.
Application Example 1
The industrial carbonic acid sodium raw materials (1) that uses in this application embodiment 1 is unskilled workman's industry yellow soda ash of buying from the market, contains lead, the 0.0009wt% arsenic of 0.002wt%.
The industry five water Bismuth trinitrate raw material Bi (NO that in this application embodiment 1, use
3)
3.5H
2O (raw material 2) is unskilled workman's industry Bismuth trinitrate of buying from the market, contains 0.01wt% lead as heavy metal, the mercury of 0.0002wt%, 0.002wt% arsenic, 0.006wt% silver.
Operation steps is as follows:
One), feed purification is processed:
A1) industrial sodium carbonate (raw material 1) with 2.12kg is dissolved in the concentration that reaches 8wt% in the deionized water, with activated carbon decolorizing, the removal of impurity, filters and obtains filtrate 1; Then in the filtrate 1 that obtains, add the polyacrylamide-co-vinylbenzene-co-acrylic copolymer (II-A) of modification of above Preparation Example 1 of 0.25kg as sorbing material, by the Adsorption heavy metal; Again filter, obtain to contain the purifying filtrate 1 ' of yellow soda ash;
A2) with the five water Bismuth trinitrate (Bi(NO of 4.851kg
3)
35H
2O) (raw material 2) is dissolved in the concentration that reaches 10wt% in the dilute nitric acid solution of 0.5wt% concentration, with activated carbon decolorizing, the preliminary removal of impurity, filters and obtains filtrate; Then in filtrate, add the polyacrylamide-co-vinylbenzene-co-acrylic copolymer (II-A) of modification of above Preparation Example 1 of 0.5kg as sorbing material, by the Adsorption heavy metal; Again filter, obtain to contain the purifying filtrate 2 of Bismuth trinitrate;
Two), Bismuth Subcarbonate is synthetic:
Mol ratio according to yellow soda ash and Bismuth trinitrate is 2:1, and filtrate 1 ' and filtrate 2 are joined in the reactor, regulates pH value between 8-10 with sodium hydroxide or salpeter solution, stirs under 45 ℃ temperature and reacts 20 minutes, and formation contains sedimentary mixture;
Three), aftertreatment:
Carry out rinsing to containing sedimentary mixture, drying is pulverized, and obtains Bismuth Subcarbonate (BiO)
2CO
31/2H
2The O solid product.
The purifying Bismuth Subcarbonate (BiO) that this application embodiment 1 obtains
2CO
31/2H
2The O solid product has following assay
(100g sample):
The modified copolymer of the present invention that the data declaration of upper table contains N and S has the effect that mercury is removed in desirable absorption.
Application Example 2
The industrial carbonic acid sodium raw materials (1) that uses in this application embodiment 2 is unskilled workman's industry yellow soda ash of buying from the market, contains lead, the 0.0009wt% arsenic of 0.002wt%.
The industry five water Bismuth trinitrate raw material Bi (NO that in this application embodiment 2, use
3)
3.5H
2O (raw material 2) is unskilled workman's industry Bismuth trinitrate of buying from the market, contains 0.02wt% lead as heavy metal, 0.0003wt% mercury, 0.004wt% arsenic (in arsenate), 0.006wt% silver.
Repeated application embodiment 1, just uses the modified copolymer II-E of Preparation Example 5.
The purifying Bismuth Subcarbonate (BiO) that this application embodiment 2 obtains
2CO
31/2H
2The O solid product has following assay:
The data declaration load of upper table metal oxide MnO
2Modified copolymer of the present invention have the effect that arsenic is removed in desirable absorption.
Can find out from Application Example 1 and 2, modified copolymer of the present invention is suitable for producing highly purified Bismuth Subcarbonate from the industrial sodium carbonate of heavy metal severe contamination and industrial nitric acid bismuth.
Application Example 3 (contrast)
Repeated application embodiment 2, just replace its employed modified copolymer II-E, use the unmodified multipolymer I in the Preparation Example 1 in this application embodiment 3.
The purifying Bismuth Subcarbonate (BiO) that this application embodiment 3 obtains
2CO
31/2H
2The O solid product has following assay:
As can be seen from the above table, product has the heavy-metal residual of trace.
Claims (9)
1. prepare the method for Bismuth Subcarbonate from industrial sodium carbonate and industrial nitric acid bismuth, the method comprises:
(A), feed purification is processed:
A1) industrial sodium carbonate is dissolved in the concentration that reaches 2-30wt% in the deionized water, with activated carbon decolorizing, the removal of impurity, filters and obtain filtrate 1; Randomly, then in the filtrate 1 that obtains, add the polyacrylamide of modification-co-vinylbenzene-co-acrylic copolymer as sorbing material, by the Adsorption heavy metal; Again filter, obtain to contain the purifying filtrate 1 ' of yellow soda ash;
A2) the industrial nitric acid bismuth is dissolved in the concentration that reaches 2-30wt% in the dilute nitric acid solution, with activated carbon decolorizing, the preliminary removal of impurity, filters and obtain filtrate; Then in filtrate, add the polyacrylamide of modification-co-vinylbenzene-co-acrylic copolymer as sorbing material, by the Adsorption heavy metal; Again filter, obtain to contain the purifying filtrate 2 of Bismuth trinitrate;
(B), Bismuth Subcarbonate is synthetic:
Mol ratio according to yellow soda ash and Bismuth trinitrate is 6:1 to 3:2, filtrate 1 or filtrate 1 ' are joined in the reactor with filtrate 2, in the situation that heat up or do not heat up, at 7.5-12 (preferred 8-11.5, more preferably 9-11) stirs in the pH scope and react, form and contain sedimentary mixture;
(C), aftertreatment:
Carry out rinsing to containing sedimentary mixture, drying is pulverized, and obtains Bismuth Subcarbonate (BiO)
2CO
31/2H
2The O solid product;
Wherein, substep a1 in step (A)) employed modified copolymer is by with formaldehyde and dimethyl amine and the optional C2-C4 organic amine that contains sulfydryl polyacrylamide-co-vinylbenzene-co-acrylic acid copolymer raw material being carried out modification, introduces methylol (CH at the side chain of multipolymer or a2)
2-OH) and amine methyl (CH
2-N (CH
3)
2), and randomly the side chain of multipolymer introduce or do not introduce sulfydryl (SH) or sulfenyl (S-), obtain.
2. according to claim 1 method wherein, is carried out repeatedly rinsing in step (C), and the pH value that makes washing water is till (preferably between 8-10, for example 8.5) between the 7.5-11.
3. according to claim 1 and 2 method, the wherein weight ratio of three kinds of monomers of the polyacrylamide of modification-co-vinylbenzene-co-acrylic copolymer, i.e. acrylamide: vinylbenzene: vinylformic acid, for: 70-90:7-22:1-5.
4. the method for any one according to claim 1-3 wherein contains the methylol (CH of 0.5-15wt% in the modified copolymer
2-OH) and the amine methyl (CH of 0.5-15wt%
2-N (CH
3)
2), and optional, 0% or the sulfydryl of 0.5-6wt% (SH) or sulfenyl-S-, based on the gross weight of multipolymer.
5. the method for any one according to claim 1-4, wherein also contain in the modified copolymer or load the Fe of 0.2-5wt%
3O
4, MnO
2And/or ZrO
2
6. the method for any one according to claim 1-5, wherein the mol ratio according to yellow soda ash and Bismuth trinitrate is 5:1 to 3.5:2, more preferably 4:1 to 2:1 in step (B).
7. the method for any one according to claim 1-6, wherein the weight-average molecular weight of modified copolymer is in 5-40 ten thousand daltonian scopes.
8. the method for any one according to claim 1-7, wherein in substep (a1) when adding modified copolymer, the addition of modified copolymer is the 1-20wt% that is equivalent to the total consumption of industrial sodium carbonate.
9. the method for any one according to claim 1-8, wherein the addition of modified copolymer is the 1-40wt% that is equivalent to the total consumption of industrial nitric acid bismuth in substep (a2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310319736.0A CN103359789B (en) | 2013-07-26 | 2013-07-26 | Preparation method of bismuth subcarbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310319736.0A CN103359789B (en) | 2013-07-26 | 2013-07-26 | Preparation method of bismuth subcarbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103359789A true CN103359789A (en) | 2013-10-23 |
| CN103359789B CN103359789B (en) | 2014-03-12 |
Family
ID=49362167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310319736.0A Active CN103359789B (en) | 2013-07-26 | 2013-07-26 | Preparation method of bismuth subcarbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103359789B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031200A (en) * | 2014-06-03 | 2014-09-10 | 京东方科技集团股份有限公司 | High-polymer dye compound, and light-sensitive resin composition and application thereof |
| CN104399502A (en) * | 2014-10-27 | 2015-03-11 | 重庆工商大学 | Lattice defect-containing difunctional bismuth subcarbonate catalyst and preparation method thereof |
| CN105268462A (en) * | 2015-07-03 | 2016-01-27 | 西南石油大学 | Preparation method of nitrogen doped bismuth-containing oxides at low temperature |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100092378A1 (en) * | 2007-04-25 | 2010-04-15 | Seung Wok Han | Method of preparing bismuth oxide and apparatus therefor |
| CN101817555A (en) * | 2010-03-25 | 2010-09-01 | 山东大学 | Bismuthyl carbonate micro flowery material with graded structure and preparation method thereof |
| CN103011286A (en) * | 2012-12-27 | 2013-04-03 | 湖南金旺铋业股份有限公司 | Process for producing bismuth subcarbonate with crude bismuth oxide |
-
2013
- 2013-07-26 CN CN201310319736.0A patent/CN103359789B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100092378A1 (en) * | 2007-04-25 | 2010-04-15 | Seung Wok Han | Method of preparing bismuth oxide and apparatus therefor |
| CN101817555A (en) * | 2010-03-25 | 2010-09-01 | 山东大学 | Bismuthyl carbonate micro flowery material with graded structure and preparation method thereof |
| CN103011286A (en) * | 2012-12-27 | 2013-04-03 | 湖南金旺铋业股份有限公司 | Process for producing bismuth subcarbonate with crude bismuth oxide |
Non-Patent Citations (1)
| Title |
|---|
| 李德良等: "超细高纯氧化铋的制备研究", 《无机盐工业》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031200A (en) * | 2014-06-03 | 2014-09-10 | 京东方科技集团股份有限公司 | High-polymer dye compound, and light-sensitive resin composition and application thereof |
| CN104031200B (en) * | 2014-06-03 | 2016-06-15 | 京东方科技集团股份有限公司 | A kind of high molecular dye compound and photosensitive polymer combination thereof and application |
| US9683103B2 (en) | 2014-06-03 | 2017-06-20 | Boe Technology Group Co., Ltd. | Polymeric dye compound, photosensitive resin composition comprising same and use thereof |
| CN104399502A (en) * | 2014-10-27 | 2015-03-11 | 重庆工商大学 | Lattice defect-containing difunctional bismuth subcarbonate catalyst and preparation method thereof |
| CN104399502B (en) * | 2014-10-27 | 2016-07-06 | 重庆工商大学 | Difunctional bismuthyl carbonate Catalysts and its preparation method containing lattice defect |
| CN105268462A (en) * | 2015-07-03 | 2016-01-27 | 西南石油大学 | Preparation method of nitrogen doped bismuth-containing oxides at low temperature |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103359789B (en) | 2014-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sun et al. | Biosorption of antimony (V) by freshwater cyanobacteria Microcystis biomass: chemical modification and biosorption mechanisms | |
| US6132624A (en) | Method for treating waste water | |
| CN103395815B (en) | Preparation method for preparing high-purity calcium chloride from industrial calcium chloride | |
| CN102935352B (en) | Method for absorbing and removing heavy metal and hexavalent chromium from waste liquid by using mangosteen slag | |
| CN103301803A (en) | Preparation method of attapulgite-modified clay for ammonia-nitrogen wastewater treatment | |
| CN111939875B (en) | Targeted silica gel material adsorbent and application thereof | |
| CN103359789B (en) | Preparation method of bismuth subcarbonate | |
| CN103071458A (en) | Silane-functionalized delaminated hydrotalcite, and preparation method and application of hydrotalcite | |
| CN101680050B (en) | Method of manufacturing fe and ni containing material, ferronickel mass using the fe and ni containing material and method for manufacturing the ferronickel mass | |
| CN103342722B (en) | Preparation method of alkaline bismuth gallate | |
| CN103395808B (en) | Preparation method of aluminum magnesium carbonate | |
| Karagianni et al. | Enhanced Hg removal from aqueous streams by sulfurized activated carbon products: Equilibrium and kinetic studies | |
| TW576825B (en) | Method for liquid chromate ion and oxy-metal ions removal and stabilization | |
| KR102225373B1 (en) | Method for preparing a composition for adsorbing cesium using chitin | |
| JP3227517B2 (en) | Treatment method for phosphorus-containing wastewater | |
| US3970553A (en) | Heavy metal adsorbent process | |
| CN113952940B (en) | Preparation method of surface imprinting microsphere adsorption material for selectively removing Sb ions | |
| CN107096501B (en) | Iron ion loaded activated carbon for adsorbing xanthate and preparation method and adsorption method thereof | |
| CN111547777B (en) | Method for removing arsenic in contaminated acid by ferroferric oxide/kaolin nanocomposite | |
| JP3240442B2 (en) | Granulated dephosphorizing agent and wastewater treatment method | |
| CN102126735A (en) | Method for extracting tschermigite from coal gangue or stone coal | |
| CN110975797A (en) | Iron-based argillaceous limestone-based mercury advanced treatment material and preparation method and application thereof | |
| SU707592A1 (en) | Granulated sorbent for arsenic extraction | |
| Mabuka | The recovery of valuable base metals from electronic waste using a biological matrix extracted from Black soldier flies | |
| Parajuli | Doctor of Engineering |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |